1. Field of the Invention
The present invention relates to a new class of useful polymers which contain both carbonyl groups and oxycarbonyl groups in the polymer chain. More specifically, the poly(keto-esters) of the invention have carbonyl and oxycarbonyl units randomly combined in a straight-chain arrangement with linking units derived from olefinic monomers.
2. Description of Related Art
Polyketones, i.e., polymers having carbonyl groups incorporated in the polymer chain, are known. They are most commonly produced by polymerizing carbon monoxide with one or more .alpha.-olefins. Polyketones of this type derived from ethylene and carbon monoxide are disclosed by Brubaker in U.S. Pat. No. 2,495,286. Numerous other liquid and gas phase procedures utilizing Ziegler and radical catalysts have been described in the prior art for polymerizing carbon monoxide with ethylene and other olefinically unsaturated monomers. A general review of the properties, preparations, reactions and uses of olefin-carbon monoxide copolymers can be found in the Encyclopedia of Polymer Science and Technology, Vol. 9, p. 397-402, John Wiley & Sons, Inc.(1968).
Polyketones obtained by the copolymerization of carbon monoxide and functionalized vinyl monomers having pendant functional groups are also known. The copolymerization of carbon monoxide with vinyl halides, most commonly vinyl chloride, is reported by Wescott et al in Macromolecules 17, 2501 (1984), Kawai et al in J. Polym. Sci., A-1 10, 1709 (1972) Weintraub et al in Chem. Ind. 1976 (1965) and in U.S. Pat. No. 3,790,460; Kawai et al in J. Polym. Sci., Polym. Chem. Ed. 12, 1041 (1974) disclose the copolymerization of carbon monoxide with styrene and vinyl chloride Methyl methacrylate, acrylonitrile, vinyl chloride, vinylidene chloride and styrene have also been copolymerized with carbon monoxide using azobisisobutyronitrile catalyst by Otsuka et al in Die Makromolekulare Chemie 103, 291 (1967). Terpolymers of carbon monoxide, ethylene and vinyl acetate are disclosed in U.S. Pat. Nos. 4,172,939, 4,137,382 and 3,780,140. Additionally, in U.S. Pat. No. 3,780,140 the terpolymerization of ethylene and carbon monoxide with methyl methacrylate, vinyl propionate, methyl vinyl ether and isobutyl acrylate is described European Patent Application EP 281139A2 discloses terpolymers of ethylene, carbon monoxide and maleic anhydride.
Other methods are known for the preparation of polyketones and include, for example, copolymerization of ethylene with aliphatic aldehydes at high temperature and pressure; oxidation of polyvinylalcohol or polyethylene; cationic polymerization of ketene or diketene; radical ring-opening polymerization of unsaturated cyclic ethers or diketene; and radical ring-opening polymerization of 2,2-diphenyl-4-methylene-1,3-dioxolane.
Various procedures are known to chemically modify polyketones. U.S. Pat. No. 2,457,271 discloses a method for modifying monoolefin-carbon monoxide copolymers to increase the degree of unsaturation by heating the copolymer in a solution of an organic solvent with a minor amount of an alkali metal hydroxide. The copolymer is reacted until the oxygen content is decreased by at least 5% or the iodine number increased to at least 25. Modification of polyketones (monoolefin-carbon monoxide copolymers) by reaction with hydrazine hydrate and related nitrogen-containing compounds is described in U.S. Pat. No. 2,457,279. A process for reacting polyketones with hydrogen cyanide to prepare polycyanohydrin resins is disclosed in U.S. Pat. No. 2,495,284.
U.S. Pat. No. 2,495,292 discloses the catalytic hydrogenation of monoolefin-carbon monoxide polymers in the presence of a nickel catalyst to reduce the carbonyl groups to secondary alcohol groups and obtain high molecular weight polyhydric alcohols. U.S. Pat. No. 2,846,406 relates to a process for reacting monoolefin-carbon monoxide copolymers with formaldehyde and specific ammonium or amine salts to produce polyamines of relatively high molecular weight. Another process for modifying monoolefin-carbon monoxide copolymers by reaction with hydrazoic acid in the presence of an acid catalyst is disclosed in U.S. Pat. No. 3,068,201.
Processes for producing thermoplastic polymers from polyketones are also disclosed in U.S. Pat. Nos. 3,979,373 and 3,979,374. The products of U.S. Pat. No. 3,979,373 are polymeric furan derivatives obtained by reacting an equimolar alternate copolymer of ethylene and carbon monoxide with a strong acid, e.g. sulfuric, phosphoric, p-toluene sulfonic, etc., at 40.degree.-200.degree. C. The polymeric pyrrollic polymers of U.S. Pat. No. 3,979,374 are obtained by reacting an equimolar alternate copolymer of ethylene and carbon monoxide with a primary monoamine in the presence of strong acid and a solvent at a temperature from 40.degree.-100.degree. C.
U.S. Pat. Nos. 4,616,072 and 4,687,805 disclose halogenating ethylene-carbon monoxide copolymers by contacting said copolymers in a liquid medium and in the presence of an anionic halogenation catalyst selected from Lewis acids and Lewis bases.
The oxidation and chain cleavage of ethylene-carbon monoxide copolymers to produce mixtures of .alpha., .omega.- dicarboxylic acids ranging from succinic acid through dodecanedioic acid and possibly higher and their corresponding esters is disclosed in U.S. Pat. No. 2,436,269. The oxidation is typically accomplished utilizing nitric acid and a vanadium oxidation catalyst, e.g. vanadium pentoxide or ammonium vanadate. Other oxidizing agents which are disclosed include the higher oxides of nitrogen, chromic acid, permanganates, molecular oxygen or air, or mixtures of these.
Poly(keto-esters) having ester groups pendant to the polymer chain are known and can be obtained by polymerizing carbon monoxide with alkyl acrylates or methacrylates as previously described. Optionally, other olefinic comonomers may be included in the polymerization. They can also be produced in accordance with the procedure of U.S. Pat. No. 2,557,256 by polymerizing carbon monoxide with a polymerizable olefinic compound containing ethylenic unsaturation and an alcohol or alkyl formate. Poly(keto-esters) having terminal ester groups are obtained by the palladium (II)-catalyzed copolymerization of carbon monoxide with ethylene in alcoholic solvents as disclosed by T. Lai et al in Organometallics, 3, 866-870(1984).
Poly(keto-esters) having keto and ester groups uniformly distributed throughout are also known. Such polymers can be produced by the ring-opening polymerization of unsaturated spiro ortho esters as disclosed by T. Endo et al in J. Polym. Sci: Polym. Chem. Ed., Vol 19, 1283 (1981). It is also known that numerous other poly(keto-esters) can be produced by the condensation polymerization of keto-dicarboxylic acids with diols. While the resulting condensation polymers will have both ester and keto groups in the polymer chain, the groups are necessarily fixed in relation to each other and uniformly located throughout the polymer backbone. Illustrative keto-containing diacids and diols which can be used include .gamma.-ketopimelic acid, .alpha.-oxoglutaric acid, oxalacetic acid, ethylene glycol, butanediol and hexanediol